JP2023020191A - Method for manufacturing decorative plate and decorative plate - Google Patents

Abstract

To provide a method for simply manufacturing a decorative plate which is excellent in uneven feeling.SOLUTION: Step 1: Forming a release layer 20 at a part on one surface side of a first base material 10. An area where the release layer is formed in one surface of the first base material is represented by A1, and an area where the release layer is not formed is represented by A2. A first laminate 100 is obtained by forming a resin layer 30 in the second region. As the first base material, a water-soluble base material or a water-permeable base material is used. Step 2: A second laminate 300 is obtained by overlapping a second base material 200 containing a resin-impregnated base material impregnated with an uncured thermosetting resin on a surface on a side opposite to the side having the release layer of the first laminate. Step 3: Infiltrating a part of the uncured thermosetting resin into a resin layer of the second area by hot pressing the second laminate in the state where both surfaces of the second laminate are sandwiched between mirror surface plates. Step 4: Taking out the second laminate of the mirror surface plates, and a decorative plate is obtained.SELECTED DRAWING: Figure 4

Description

TECHNICAL FIELD The present disclosure relates to a decorative laminate manufacturing method and a decorative laminate.

Decorative panels having excellent strength, hardness, heat resistance, and the like are sometimes laminated on the surfaces of furniture such as tables and counters, and residential building materials such as walls and floors. Such decorative boards include thermosetting resin decorative boards such as high-pressure melamine resin decorative boards, low-pressure melamine resin decorative boards, diallyl phthalate resin decorative boards, polyester decorative boards, guanamine resin decorative boards, and phenolic resin decorative boards.

A decorative board such as a thermosetting resin decorative board is required to have a design showing a sense of quality. For example, by forming an uneven shape on the surface of the decorative board and imparting a visual three-dimensional effect to the decorative board, the decorative board is given a high-class feeling.
As a decorative board having an uneven surface, an embossed decorative board has been proposed (see Patent Documents 1 and 2, for example).

However, the embossing process as in Patent Documents 1 and 2 requires an embossing plate for each pattern, which is costly and difficult to manufacture. Moreover, the decorative laminates of Patent Documents 1 and 2 have the problem that it is difficult to synchronize the embossed concave-convex shape with the pattern, and it is difficult to impart a high degree of designability.

On the other hand, as a decorative board having an uneven surface without using an embossing plate, a decorative board of Patent Document 3 is proposed.

JP 2015-193209 A JP 2017-87544 A WO2016/148091

The decorative board of Patent Document 3 includes a paper base material, a release layer containing a cured product of an ionizing radiation curable resin provided on a part of the surface of the paper base material, and a release layer provided on the remaining part of the surface of the paper base material. and a surface layer containing a cured melamine resin. The decorative board of Patent Document 3 includes a step of providing a release layer on a part of the surface of a paper base material, impregnating the paper base material with an uncured melamine resin, and coating the release layer with the uncured melamine resin. After heating, the uncured melamine resin is thermally cured, and the cured resin layer covering the release layer is peeled off. As a result, in the decorative board of Patent Document 3, an elevation difference is formed between a part having a release layer and a part not having a release layer, and an uneven surface shape is formed.
In the method for producing a decorative board of Patent Document 3, after obtaining a laminate containing a paper substrate, a release layer, and a cured product layer of a melamine resin, the cured resin layer covering the release layer is peeled off from the laminate. have a step of In the method for manufacturing a decorative board of Patent Document 3, there is a problem that the peelability in the step of peeling off the cured resin layer covering the release layer differs depending on the material of the paper base material. If the releasability is different, it becomes difficult to stabilize the quality of the obtained decorative laminate. Even when the paper base material is changed, the peelability can be adjusted by changing the materials of other layers constituting the decorative board or by changing the manufacturing conditions. labor intensive.

The present disclosure has been made under such circumstances, and an object of the present disclosure is to provide a method for easily manufacturing a decorative board having an excellent feeling of unevenness, and a decorative board having an excellent feeling of unevenness.

In order to solve the above problems, the present disclosure provides the following [1] to [2] decorative boards and methods for manufacturing the decorative boards.
[1] A method for manufacturing a decorative panel, comprising the following steps 1 to 4.
Step 1: A release layer is formed on a portion of one side of the first base material. In the one surface of the first base material, the region where the release layer is formed is defined as a first region, and the region where the release layer is not formed is defined as a second region. By forming a resin layer in the second region on the one surface side of the first substrate, a first laminate having the first substrate, the release layer and the resin layer is obtained. As the first base material, a water-soluble base material or a water-permeable base material is used.
Step 2: By stacking a second base material containing a resin-impregnated base material impregnated with an uncured thermosetting resin on the surface of the first laminate opposite to the side having the release layer, the second base material is 2 Laminates are obtained.
Step 3: Both surfaces of the second laminate are sandwiched between mirror plates and then hot-pressed to allow part of the uncured thermosetting resin to pass through the first substrate, and the first substrate A portion of the uncured thermosetting resin that has permeated the material is allowed to soak into the resin layer of the second region.
Step 4: Take out the second laminate from between the mirror plates to obtain a decorative plate.
[2] A decorative laminate having one or more layers on a substrate,
The decorative plate has a first region and a second region in the plane,
A decorative board that satisfies the following conditions 1 and 2 when the outermost surface of the side of the decorative board having one or more layers is defined as the first surface.
<Condition 1>
Among the layers constituting the first surface, n1 is the refractive index of the resin contained in the layer corresponding to the first region, and n2 is the refractive index of the resin contained in the layer corresponding to the second region. , n1≠n2.
<Condition 2>
Regarding the elevation of the first surface, the elevation difference between the elevation of the location corresponding to the first region and the elevation of the location corresponding to the second region is more than 1.0 μm and 5.0 μm or less.

According to the present disclosure, it is possible to easily manufacture a decorative board with excellent texture. In addition, according to the present disclosure, it is possible to provide a decorative sheet with excellent unevenness.

1 is a schematic perspective view showing one embodiment of a decorative board of the present disclosure; FIG. 1 is a schematic cross-sectional view showing an embodiment of a decorative board of the present disclosure; FIG. FIG. 2 is a schematic cross-sectional view showing one embodiment of a state in which a first laminate is obtained in relation to the method for manufacturing a decorative laminate of the present disclosure; FIG. 4 is a schematic cross-sectional view showing one embodiment of a state in which a second laminate is obtained in relation to the method for manufacturing a decorative laminate of the present disclosure.

[Decorative board]
The decorative sheet of the present disclosure has one or more layers on a base material, has a first region and a second region in the plane of the decorative sheet, and has the uppermost layer on the side of the decorative sheet having the one or more layers. When the surface is defined as the first surface, the following conditions 1 and 2 are satisfied.
<Condition 1>
Among the layers constituting the first surface, n1 is the refractive index of the resin contained in the layer corresponding to the first region, and n2 is the refractive index of the resin contained in the layer corresponding to the second region. , n1≠n2.
<Condition 2>
Regarding the elevation of the first surface, the elevation difference between the elevation of the location corresponding to the first region and the elevation of the location corresponding to the second region is more than 1.0 μm and 5.0 μm or less.

FIG. 1 is a schematic perspective view showing one embodiment of the decorative board of the present disclosure, and FIG. 2 is a schematic cross-sectional view showing one embodiment of the decorative board of the present disclosure. The decorative laminate 500 of FIGS. 1 and 2 has a layer 90 on a substrate 80 . In addition, the decorative plate 500 of FIGS. 1 and 2 has a first area A1 and a second area A2 in the plane. In FIG. 1, symbol S1 indicates the outermost surface of the side of the decorative board having one or more layers.
In FIG. 2 , the layer 90 includes the release layer 20 , the primer layer 30 and the first pattern layer 41 at the location corresponding to the first area A<b>1 . In FIG. 2, a portion corresponding to the second area A2 has the primer layer 30 and the second pattern layer 42 as the layer 90 . In FIG. 2, symbol h indicates the difference in elevation between the elevation of the first surface at the location corresponding to the first region and the elevation of the first surface at the location corresponding to the second region.

The shape of the decorative laminate of the present disclosure is not particularly limited. Examples of the shape of the decorative board include a flat plate shape, a shape having a curved surface, a three-dimensional three-dimensional shape, and the like. It is preferable that the shape of the decorative board is flat in order to make the manufacture of the decorative board easier.

The decorative laminate of the present disclosure needs to satisfy Conditions 1 and 2 when the outermost surface on the side having one or more layers is defined as the first surface.

<Condition 1>
In condition 1, among the layers constituting the first surface, the refractive index of the resin contained in the layer corresponding to the first region was defined as n1, and the refractive index of the resin contained in the layer corresponding to the second region was defined as n2. In this case, it is specified that n1≠n2.

By satisfying Condition 1, a difference can be generated between the surface reflectance of the first region and the surface reflectance of the second region, so that a difference in brightness is generated between the first region and the second region. be able to. Due to this contrast difference, even if the difference in elevation between the first area and the second area is not sufficient, the texture of the surface of the decorative board can be improved.

As for the magnitude relationship between n1 and n2, n1 may be larger or n2 may be larger. Regardless of which of n1 and n2 is large, a difference in brightness based on the difference in reflectance can be generated between the first region and the second region, so that the unevenness of the surface of the decorative plate can be improved. .
Embodiments in which the higher refractive index of the first region and the second region is also preferred. According to such an embodiment, the region with the higher altitude can be felt to be higher, and the unevenness of the surface of the decorative plate can be easily improved.

It is preferable to increase the difference between n1 and n2 in order to improve the feeling of unevenness on the surface of the decorative sheet. |n1-n2| is preferably 0.02 or more, more preferably 0.05 or more, more preferably 0.07 or more, more preferably 0.10 or more, It is more preferably 0.12 or more.
|n1-n2| It is preferably 0.20 or less, more preferably 0.18 or less, and even more preferably 0.16 or less.
n1 and n2 can be determined, for example, by the method described in Examples.
In this specification, the refractive index difference means the refractive index at a wavelength of 589 nm unless otherwise specified.

The values of n1 and n2 depend on the type of resin contained in the layer corresponding to the first region among the layers constituting the first surface and the layer corresponding to the second region among the layers constituting the first surface. It can be adjusted according to the type of resin used.
In the manufacturing method of the decorative board of the present disclosure, which will be described later, part of the uncured thermosetting resin that has passed through the first base material permeates into the resin layer in the second region. Therefore, among the layers forming the first surface, the layer corresponding to the second region contains an uncured thermosetting resin. On the other hand, in the first region, the release layer suppresses penetration of the uncured thermosetting resin that has passed through the first base material. Therefore, among the layers constituting the first surface, the layer corresponding to the first region contains almost no uncured thermosetting resin. In this way, in the manufacturing method of the decorative laminate of the present disclosure, which will be described later, a difference is generated between n1 and n2.

The reason why the surface reflectance of the first region and the surface reflectance of the second region are different when Condition 1 is satisfied will be described below.

When the refractive index of air is n0 and the incident angle of light from the air to the surface of the first region is _φ0 , the surface reflectance R1 of the first region is expressed by the following formula 1′ from n0, n1 and _φ0 . and Equation 1''. R1 _P and R1 _S are the reflectance for the P-polarized component and the reflectance for the S-polarized component, respectively.
R1 _P = tan ² {φ ₀ −sin ⁻¹ (n0sinφ ₀ /n1)}/tan ² {φ ₀ +sin ⁻¹ (n0sinφ ₀ /n1)} [Formula 1′]
R1 _S = sin ² (φ ₀ −sin ⁻¹ (n0sinφ ₀ /n1))/sin ² (φ ₀ +sin ⁻¹ (n0sinφ ₀ /n1)) [Formula 1″]

The above formula is well known in the field of optics, and is described, for example, in the following literature.
"Science Library Physics = 9 Optics" Published September 30, 1980, 2nd edition, published by Science Co., Ltd., pp. 20-29

Similarly, if the incident angle of light from the air onto the surface of the second region is _φ0 , then from n0, n2 and _φ0 , the surface reflectance R1 of the second region is given by the following formulas 2′ and 2″ can be expressed as R2 _P and R2 _S are the reflectance for the P-polarized component and the reflectance for the S-polarized component, respectively.
R2 _P = tan ² {φ ₀ −sin ⁻¹ (n0sinφ ₀ /n2)}/tan ² {φ ₀ +sin ⁻¹ (n0sinφ ₀ /n2)} [Formula 2′]
R2 _S = sin ² (φ ₀ −sin ⁻¹ (n0sinφ ₀ /n2))/sin ² (φ ₀ +sin ⁻¹ (n0sinφ ₀ /n2)) [Formula 2″]

When the incident angle φ ₀ of light to the first region and the second region is 0 degrees, there is no distinction between P-polarized light and S-polarized light, and the reflectance of the first region and the reflectance of the second region are given by the following equation 1 ''' and Equation 2'''.

Reflectance of light on the surface of the first region R1=(n1-n0)/(n1+n0) [Equation 1''']
Reflectance of light on the surface of the second region R2=(n2-n0)/(n2+n0) [Equation 2''']

Since the refractive index of air is approximately 1, when approximating with n0=1, [Formula 1'''] and [Formula 2'''] can be further approximated by Formulas 1A and 2A below.

Reflectance of light on the surface of the first region R1=(n1−1)/(n1+1) [Formula 1A]
Reflectance of light on the surface of the second region R2=(n2−1)/(n2+1) [Formula 2A]

As is clear from the above equations, R1<R2 when n1<n2, and R1>R2 when n1>n2.

<Condition 2>
In condition 2, regarding the altitude of the first surface, the altitude difference between the altitude of the location corresponding to the first region and the altitude of the location corresponding to the second region is more than 1.0 μm and 5.0 μm or less. stipulates.

If the elevation of the surface of the veneer is too uniform, the veneer tends to look like an artifact. Therefore, in condition 2, by setting the altitude difference to be more than 1.0 μm, the feeling of an artificial object can be suppressed, and it is possible to easily feel like a natural object.
If there is too much difference in altitude on the surface of the decorative sheet, the appearance of unevenness based on the refractive index difference in Condition 1 may be impaired. Therefore, in Condition 2, by setting the altitude difference to 5.0 μm or less, it is possible to improve the unevenness of the surface of the decorative board.
In addition, if there is too much difference in altitude on the surface of the decorative board, dirt tends to accumulate in the recesses on the surface of the decorative board, and the antifouling property tends to decrease. For this reason, setting the difference in elevation to 5.0 μm or less in condition 2 is preferable in terms of easily improving the antifouling property.
The altitude difference of Condition 2 is preferably 1.5 μm or more and 4.5 μm or less, more preferably 2.0 μm or more and 4.0 μm or less.

As used herein, the term "elevation" means the thickness direction of the decorative board. In FIGS. 1 and 2, the z direction corresponds to the thickness direction of the decorative board. Moreover, in FIG. 2, the symbol h indicates the altitude difference of Condition 2.
The difference between the altitude of the first area and the altitude of the second area can be determined, for example, by the method described in the examples.

As for the magnitude relationship between the altitude of the first area and the altitude of the second area, the altitude of the first area may be higher, or the altitude of the second area may be higher. Satisfying the conditions 1 and 2 makes it possible to improve the unevenness of the surface of the decorative board regardless of whether the altitude of the first region or the altitude of the second region is high.
The elevation difference in condition 2 can be adjusted by the difference between the total thickness of the layers formed in the first region and the total thickness of the layers formed in the second region.

<Arrangement of first area and second area>
Although the arrangement of the first region and the second region in the plane of the decorative board is arbitrary, it is preferable to set the areas and patterns of both as follows.

-area-
On the first surface of the decorative board, the area of the first region is defined as S1, and the area of the second region is defined as S2. The ratio of S1 and S2 to the first surface of the decorative laminate can be adjusted according to the desired design.
The total ratio of S1 and S2 to the total area of the first surface is preferably 80% or more, more preferably 90% or more, and most preferably 100%, in order to improve the texture. preferable.

The ratio [S1/S2] between S1 and S2 can be adjusted according to the desired design properties, but is preferably 0.10 or more and 9.00 or less, and 0.25 or more, in order to improve the feeling of unevenness. It is more preferably 4.00 or less, and further preferably 0.40 or more and 2.50 or less.

―pattern, pattern―
In order to improve designability, it is preferable to form a predetermined pattern with two regions, the first region and the second region.
The predetermined pattern includes a wood grain pattern, a marquetry pattern, a stone grain pattern, a tiled pattern, a cloth pattern, a leather pattern, a grain pattern, a geometric pattern, and the like. For example, a wood grain pattern can be formed by combining the pattern of the first region with a wood grain conduit pattern and the pattern of the second region with a wood texture pattern.
In order to enhance the designability of the pattern, it is preferable that the first region or the second region have a pattern layer, and it is more preferable that the first region and the second region have a pattern layer.

The width and length of the first region and the second region are not particularly limited, and may be appropriately determined according to the design.

<Layer structure>
The decorative laminates of the present disclosure have one or more layers on a substrate.
The one or more layers preferably have different layer configurations in the first region and the second region. Examples of the layer structure of the first region include the following X1 to X8. The layer structure of the second region includes Y1 to Y3 below. X1 to X8 below and Y1 to Y3 below can be combined, respectively. However, the layer structures of the first region and the second region are not limited to the layer structures described below.
-Embodiment of the layer structure of the first region-
X1: single-layer configuration of release layer X2: layer configuration having a release layer and a pattern layer in this order from the substrate side.
X3: A layer structure having a release layer and a primer layer in this order from the substrate side.
X4: A layer structure having a release layer, a primer layer and a pattern layer in this order from the substrate side.
X5: A layer structure having a primer layer and a release layer in this order from the substrate side.
X6: A layer structure having a primer layer, a release layer and a pattern layer in this order from the substrate side.
X7: A layer structure having a primer layer, a release layer and a primer layer in this order from the substrate side.
X8: A layer structure having a primer layer, a release layer, a primer layer and a design layer in this order from the substrate side.
-Embodiment of the layer structure of the second region-
Y1: Single layer configuration of pattern layer Y2: Single layer configuration of primer layer Y3: Layer configuration having a primer layer and a pattern layer in this order from the substrate side.

《First Area》
Preferably, the first region has a release layer. When the first region has two or more layers, the release layer is preferably located closest to the substrate. A primer layer may be provided between the substrate and the release layer to improve adhesion.
The release layer can suppress penetration of the uncured thermosetting resin contained in the base material during the manufacturing process of the decorative board. Therefore, by having the release layer in the first region, the penetration of the uncured thermosetting resin into the first region is suppressed, while the uncured thermosetting resin does not flow into the second region. Easier to penetrate. Thereby, among the layers constituting the first surface, the composition of the resin contained in the layer corresponding to the first region can be made different from the composition of the resin contained in the layer corresponding to the second region. , the condition 1 can be easily satisfied.

-Release layer-
The release layer preferably contains a cured product of an ionizing radiation-curable resin composition.
By including the cured product of the ionizing radiation-curable resin composition in the release layer, it is possible to easily suppress the penetration of the uncured thermosetting resin into the first region, and to easily satisfy the condition 1.

The ratio of the cured product of the ionizing radiation-curable resin composition to the total solid content of the release layer is preferably 50% by mass or more, more preferably 70% by mass or more, and 90% by mass or more. It is more preferable that the content is 95% by mass or more.

The ionizing radiation-curable resin composition is a composition containing a compound having an ionizing radiation-curable functional group (hereinafter also referred to as an "ionizing radiation-curable compound"). The ionizing radiation-curable functional group is a group that cross-links and cures upon exposure to ionizing radiation, and preferably includes a functional group having an ethylenic double bond such as a (meth)acryloyl group, a vinyl group, and an allyl group. In addition, ionizing radiation means, among electromagnetic waves or charged particle beams, those having energy quanta capable of polymerizing or cross-linking molecules, usually ultraviolet rays (UV) or electron beams (EB) are used. Electromagnetic waves such as X-rays and γ-rays, and charged particle beams such as α-rays and ion beams are also included.

The ionizing radiation-curable compound can be appropriately selected and used from among polymerizable monomers and polymerizable oligomers commonly used as ionizing radiation-curable compounds.

As the polymerizable monomer, a (meth)acrylate monomer having a radically polymerizable unsaturated group in the molecule is preferable, and a polyfunctional (meth)acrylate monomer is particularly preferable. Here, "(meth)acrylate" means "acrylate or methacrylate".
Examples of polyfunctional (meth)acrylate monomers include (meth)acrylate monomers having two or more ionizing radiation-curable functional groups in the molecule and having at least a (meth)acryloyl group as the functional group, An acrylate monomer having an acryloyl group is preferable from the viewpoint of obtaining a design with a higher texture and better surface properties.

The number of functional groups of the polyfunctional (meth)acrylate is preferably 2 or more, and the upper limit is preferably 8 or less, more preferably 6 or less, and still more preferably, in order to obtain a design with a higher texture and better surface properties. is 4 or less, particularly preferably 3 or less. These polyfunctional (meth)acrylates may be used alone or in combination.

Examples of polymerizable monomers include bifunctional (meth)acrylates such as ethylene glycol di(meth)acrylate, bisphenol A tetraethoxy diacrylate, bisphenol A tetrapropoxy diacrylate, and 1,6-hexanediol diacrylate; meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, isocyanuric acid modification (Meth)acrylates having trifunctional or higher functions such as tri(meth)acrylates are preferred. Among them, dipentaerythritol-based compounds such as dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc. are used in order to obtain a design with a higher texture and better surface properties. Polymerizable monomers are preferred, dipentaerythritol penta(meth)acrylate and dipentaerythritol hexa(meth)acrylate are more preferred, and dipentaerythritol penta(meth)acrylate and dipentaerythritol hexa(meth)acrylate can be used in combination. Especially preferred.

Polymerizable oligomers include, for example, (meth)acrylate oligomers having two or more ionizing radiation-curable functional groups in the molecule and at least (meth)acryloyl groups as the functional groups. For example, urethane (meth)acrylate oligomer, epoxy (meth)acrylate oligomer, polyester (meth)acrylate oligomer, polyether (meth)acrylate oligomer, polycarbonate (meth)acrylate oligomer, acrylic (meth)acrylate oligomer, polycaprolactone urethane (meth) ) acrylate oligomer, polycaprolactone diol urethane (meth)acrylate, and the like.

The number of functional groups of the polymerizable oligomer is preferably 2 or more, and the upper limit is preferably 8 or less, more preferably 6 or less, and still more preferably 4 or less, in order to obtain a design with a higher texture and better surface properties. Especially preferably, it is 3 or less.

The weight-average molecular weight of the polymerizable oligomer is preferably 500 or more, more preferably 1,000 or more, in order to achieve a design with a higher texture and better surface properties, and to facilitate the formation of a release layer. The upper limit is preferably 80,000 or less, more preferably 50,000 or less. As used herein, the weight average molecular weight is the average molecular weight measured by GPC analysis and converted to standard polystyrene.

When the ionizing radiation-curable resin composition is of the UV-curable type, the ionizing radiation-curable resin composition preferably contains a photopolymerization initiator.

The release layer preferably contains a reactive release agent such as a reactive silicone compound and a reactive fluorine compound. By including a reactive release agent in the release layer, it is possible to more easily suppress impregnation of the uncured thermosetting resin into the first region, so that Condition 1 can be more easily satisfied. Among the reactive release agents, a reactive silicone compound is preferred.

Examples of reactive silicone compounds include those having a polysiloxane structure as a basic structure and further having at least one reactive functional group. As the reactive functional group, an ionizing radiation-curable functional group is preferred.

The reactive silicone compound is preferably a modified silicone oil having an organic group introduced to at least one of its side chain or terminal, more preferably a modified silicone oil having an organic group introduced to both terminals. As the organic group, reactive functional groups such as (meth)acrylic group, amino group, epoxy group, mercapto group, carbinol group, phenol group, carboxyl group, etc., and polyether group are used from the viewpoint of obtaining a design with a higher texture. , an aralkyl group, a fluoroalkyl group, an alkyl group, a fatty acid amide group, a non-reactive functional group such as a phenyl group, and the like. Among them, a reactive functional group is preferable, and a (meth)acryl group is particularly preferable, that is, a (meth)acryl-modified silicone oil is particularly preferable. Moreover, these organic groups may have a substituent such as a nitrogen atom, a sulfur atom, a hydroxyl group, an alkyl group, or the like.

The content of the reactive release agent is preferably 0.1% by mass or more and 5% by mass or less, more preferably 0.5% by mass or more and 3% by mass or less, based on the total amount of the resin component forming the release layer. It is preferably 0.8% by mass or more and 2% by mass or less. When the content of the reactive release agent is within the above range, the effect of adding the reactive release agent can be efficiently obtained.

The release layer may contain fillers such as inorganic fillers and organic fillers.

The release layer may further contain additives such as ultraviolet absorbers, light stabilizers, infrared absorbers, antistatic agents, leveling agents and antifoaming agents.

Since the release layer is not formed in the second region, the height difference of Condition 2 is greatly affected by the thickness of the release layer. Therefore, it is preferable to adjust the thickness of the release layer within a range that satisfies the condition 2.
The thickness of the release layer is preferably 0.5 μm or more and 7.0 μm or less, more preferably 1.1 μm or more and 6.0 μm or less, and still more preferably 1.5 μm or more and 5.0 μm or less.

-Primer layer-
The first region may have a primer layer. The primer layer is preferably located on the opposite side of the release layer to the substrate. When the first region further has a pattern layer, it preferably has a release layer, a primer layer and a pattern layer in this order from the substrate side.
The primer layer is formed, for example, to improve adhesion between the release layer and the pattern layer.
A primer layer may be formed between the substrate and the release layer in order to improve the adhesion between the substrate and the release layer.

Examples of resin materials for forming the primer layer include urethane resins, polyester resins, acrylic resins, acrylic urethane resins, vinyl chloride-vinyl acetate copolymer resins, and the like.

The primer layer preferably does not substantially contain a cured product of the ionizing radiation-curable resin composition in order to improve adhesion. Further, by substantially not containing the cured product of the ionizing radiation-curable resin composition, in the second region, the uncured thermosetting resin can be easily impregnated into the primer layer, and the condition 1 can be easily satisfied.
As used herein, "the primer layer does not substantially contain the cured product of the ionizing radiation-curable resin composition" means that the ratio of the cured product of the ionizing radiation-curable resin composition to the total solids of the primer layer is 1 mass. % or less, preferably 0.1% by mass or less, more preferably 0.01% by mass or less, and still more preferably not containing at all.

The thickness of the primer layer is preferably 0.1 μm or more and 10 μm or less, more preferably 0.3 μm or more and 5 μm or less, and still more preferably 0.5 μm or more and 3 μm or less.

-Pattern layer-
The first area may have a pattern layer. The pattern layer is preferably located on the opposite side of the release layer to the substrate. When the first region further has a primer layer, it preferably has a release layer, a primer layer and a pattern layer in this order from the substrate side.
In this specification, the pattern layer of the first area may be referred to as the first pattern layer, and the pattern layer of the second area may be referred to as the second pattern layer.

The pattern of the first design layer is preferably synchronized with the pattern of the release layer in order to improve designability. For example, if the pattern of the gravure printing plate forming the release layer and the pattern of the gravure printing plate forming the first pattern layer are the same, the release layer and the first pattern layer can be easily synchronized. The pattern of the second pattern layer is preferably a pattern complementary to the pattern of the release layer.

The pattern layer can be formed, for example, by printing using a pattern layer ink containing a colorant and a binder resin.

Examples of coloring agents include inorganic pigments such as carbon black, iron black, titanium white, antimony white, yellow lead, titanium yellow, red iron oxide, cadmium red, ultramarine blue, and cobalt blue; Bright pigments; organic pigments such as quinacridone red, isoindolinone yellow, nickel-azo complex, phthalocyanine blue; dyes;
Binder resins include acrylic resins, styrene resins, polyester resins, urethane resins, chlorinated polyolefin resins, vinyl chloride-vinyl acetate copolymer resins, polyvinyl butyral resins, alkyd resins, petroleum resins, ketones. Examples include resins, epoxy resins, melamine resins, fluorine resins, silicone resins, cellulose derivatives, rubber resins, and the like.

The picture layer preferably does not substantially contain a cured product of the ionizing radiation-curable resin composition. Since the pattern layer does not substantially contain the cured product of the ionizing radiation-curable resin composition, the pattern layer can be easily impregnated with the uncured thermosetting resin in the second region, and the condition 1 can be easily satisfied.
In the present specification, "the pattern layer does not substantially contain the cured product of the ionizing radiation-curable resin composition" means that the ratio of the cured product of the ionizing radiation-curable resin composition to the total solids of the pattern layer is 1 mass. % or less, preferably 0.1% by mass or less, more preferably 0.01% by mass or less, and still more preferably not containing at all.

The thickness of the pattern layer can be appropriately adjusted in the range of about 0.1 μm to 20 μm in consideration of the intended design.

《Second Realm》
The second region preferably has at least one selected from a primer layer and a pattern layer.
Since the second region does not have a release layer, the uncured thermosetting resin easily penetrates into the primer layer and pattern layer of the second region. Therefore, among the layers constituting the first surface, the composition of the resin contained in the layer corresponding to the first region can be different from the composition of the resin contained in the layer corresponding to the second region. , the condition 1 can be easily satisfied.

Examples of the layer structure of the second region include a single-layer structure of a pattern layer, a single-layer structure of a primer layer, and a laminate structure having a primer layer and a pattern layer in this order from the substrate side.
The embodiment of the picture layer of the second area and the embodiment of the primer layer of the second area are the same as the embodiment of the picture layer of the first area and the embodiment of the primer layer of the first area.
The pattern layer and the primer layer of the second region preferably contain a cured product of the thermosetting resin contained in the base material.

<Base material>
The substrate is preferably one that can be impregnated with an uncured thermosetting resin during the manufacturing process of the decorative board.
Examples of the substrate include paper substrates, fiber substrates, resin substrates, etc. Among these, paper substrates and fiber substrates, which are easily impregnated with resin, are preferred, and paper substrates are more preferred.

Examples of paper substrates include kraft paper, titanium paper, linter paper, resin-impregnated paper, thin paper, and Japanese paper.
Examples of the fiber base material include non-woven fabrics and woven fabrics, for example, fiber base materials composed of inorganic fibers such as glass fiber, alumina fiber, silica fiber, carbon fiber, polyester resin, acrylic resin, polyethylene resin, and polypropylene resin. and fiber base materials composed of organic fibers of various synthetic resins, and base materials such as composites thereof.

The thickness of the base material is preferably 10 μm or more and 200 μm or less, more preferably 20 μm or more and 150 μm or less, and still more preferably 30 μm or more and 120 μm or less, for impregnation of uncured thermosetting resin, mechanical strength, and handleability. . When a paper base material is used as the base material, the basis weight is preferably 20 g/m 2 or more and 150 g/m ² or less, more preferably 30 g/m ^{2 or} more and 100 g/m ² or less, for the same purpose.

In a preferred embodiment of the decorative board of the present disclosure, the base material is preferably impregnated with an uncured thermosetting resin in the process of manufacturing the decorative board to make the base material a resin-impregnated base material. In the process of manufacturing a decorative board, a part of the thermosetting resin remains on the base material and hardens, and the other thermosetting resin permeates into the primer layer or pattern layer and hardens. Therefore, in the decorative sheet of the present disclosure, a difference in refractive index is generated between the first region and the second region, and high designability can be easily realized, and mechanical strength can be easily improved.

Curable resins impregnated into the substrate include melamine resin, urea resin, melamine-urea resin, guanamine resin, diallyl phthalate resin, polyester resin, phenol resin, epoxy resin, aminoalkyd resin, silicon resin, polysiloxane resin, and the like. It is preferably mentioned. Among these, thermosetting resins such as melamine resins, urea resins, melamine-urea resins, guanamine resins and sulfonamide resins are preferred. Among thermosetting resins, melamine resin, melamine-urea resin and phenol resin are preferred, and melamine resin is particularly preferred.

When a melamine-based resin is used as the curable resin, the following method can be used to evaluate the difference in penetration of the melamine-based resin between the first region and the second region.
Among the layers constituting the first surface, the triazine skeleton content contained in the layer corresponding to the first region is defined as TA1, and the triazine skeleton content contained in the layer corresponding to the second region is defined as T2. If TA1<TA2, it can be said that a large amount of the melamine-based resin has permeated into the layer corresponding to the second region among the layers constituting the first surface.
Even when a resin other than a melamine-based resin is used as the curable resin, the difference in penetration of the curable resin between the first region and the second region can be evaluated by quantitatively analyzing the content of the skeleton peculiar to the resin. .
The uncured thermosetting resin described above is preferably a cured product of the thermosetting resin when the decorative board is completed.

<Core layer>
The decorative laminate of the present disclosure may have a core layer on the opposite side of the substrate from the one or more layers to increase the strength of the decorative laminate.

Examples of the core layer include a fiber base material or a paper base material impregnated with an uncured resin composition containing an uncured thermosetting resin.
Examples of the types of the fiber base material and the paper base material used for the core layer include those exemplified as the base materials described above. The basis weight of the fiber base material or paper base material used for the core layer is preferably 100 g/m ² or more and 300 g/m ² or less, more preferably 150 g/m ² or more and 250 g/m ² or less.
The thermosetting resin for the core layer may be the same as those exemplified as the thermosetting resin with which the substrate is impregnated. Among thermosetting resins, phenol resins are preferred. That is, phenolic resin-impregnated paper is preferable as the core layer.

As the phenol resin-impregnated paper, for example, kraft paper having a basis weight of 150 g/m ² or more and 250 g/m ² or less is impregnated with phenol resin so that the impregnation rate is 20% or more and 60% or less, and the temperature is 100 ° C or more and 140 ° C or less. and those produced by drying with

<Water-soluble substrate or water-permeable substrate>
The decorative laminate of the present disclosure may have a water-soluble or water-permeable substrate between the substrate and one or more layers.
The water-soluble base material or water-permeable base material serves, for example, as a support when forming a release layer, a primer layer and a pattern layer. In addition, the water-soluble base material or water-permeable base material can permeate the uncured thermosetting resin contained in the base material. Therefore, condition 1 can be satisfied even if a water-soluble or water-permeable substrate is present between the substrate and one or more layers. In order to easily permeate the water-soluble or water-permeable substrate, the uncured thermosetting resin is preferably dispersed in a liquid containing water.

Among the water-soluble base material and the water-permeable base material, the water-soluble base material is preferable in that the design formed by the pattern layer is less likely to be affected because of its low color.

-Water-soluble substrate-
The water-soluble base material can be used without particular limitation as long as it is water-soluble or water-swellable. The water-soluble base material is dissolved or swelled in water so that an aqueous dispersion of an uncured thermosetting resin can permeate through the base material.

Resins constituting the water-soluble base include polyvinyl alcohol resin, dextrin, gelatin, glue, casein, shellac, gum arabic, starch, protein, polyacrylic acid amide, sodium polyacrylate, polyvinyl methyl ether, methyl vinyl ether-anhydrous. Various water-soluble resins such as maleic acid copolymer, vinyl acetate-itaconic acid copolymer, polyvinylpyrrolidone, acetyl cellulose, acetylbutyl cellulose, carboxymethyl cellulose, methyl cellulose, hydroxyethyl cellulose and sodium alginate.
These resins may be used alone, or two or more of them may be mixed and used. The water-soluble base material may contain a rubber component such as mannan, xanthan gum, or guar gum added to the water-soluble resin.

Among the above resins, polyvinyl alcohol is preferred. That is, the water-soluble substrate is preferably a polyvinyl alcohol film. The polyvinyl alcohol film may contain additives such as starch and rubber.
Polyvinyl alcohol films can be adjusted in terms of film strength, water solubility, permeability of uncured thermosetting resin, etc. by changing the degree of polymerization, degree of saponification, and blending amount of additives. can do.

The thickness of the water-soluble substrate is preferably 10 μm or more and 100 μm or less, more preferably 20 μm or more and 60 μm or less, and even more preferably 30 μm or more and 50 μm or less.
When the thickness of the water-soluble substrate is 10 μm or more, the uniformity of the film is good and the production stability is high. When the thickness of the water-soluble base material is 100 µm or less, the uncured thermosetting resin can be easily permeated.

After the decorative laminate has been manufactured, the condition and composition of the water-soluble substrate may differ from the original composition. For example, the water-soluble base material after the production of the decorative board is completed may contain a cured product of the thermosetting resin contained in the base material. Further, after the production of the decorative board is completed, part of the water-soluble resin constituting the water-soluble base material may permeate the pattern layer and the primer layer of the second region.

- Water Permeable Substrate -
The water-permeable substrate is preferably one that allows an aqueous dispersion of an uncured thermosetting resin to pass therethrough, and includes paper and fibers. Paper is preferable because it tends to improve coating suitability.

The basis weight of the paper as the water-permeable substrate is preferably 20 g/m ² or more and 100 g/m ² or less, more preferably 25 g/m ² or more and 80 g/m ² or less, and 30 g/m ² or more. It is more preferably 60 g/m ² or less.
By setting the basis weight of the paper to 20 g/m ² or more, the coating suitability can be easily improved. By setting the basis weight of the paper to 100 g/m ² or less, the permeability of the aqueous dispersion of the uncured thermosetting resin can be easily improved.

After the decorative laminate has been manufactured, the condition and composition of the water permeable substrate may differ from the original composition. For example, the water-permeable base material after the production of the decorative board is completed may contain a cured product of the thermosetting resin contained in the base material.

<Substrate>
The decorative sheet of the present disclosure may be laminated and integrated with an adherend.
The adherend is preferably located on the opposite side of the substrate from the one or more layers.
Examples of the adherend include wood board, cement board, ceramic board, metal board, resin board and FRP board.

<Application>
The decorative sheet of the present disclosure is excellent in feeling of unevenness. In addition, the decorative laminate of the present disclosure tends to have good antifouling properties. For this reason, the decorative board of the present disclosure can be used as it is, or by applying molding processing, etc., to interior materials of buildings such as top boards such as counters and desks; furniture; Used for exterior materials.

[Method for manufacturing decorative board]
The manufacturing method of the decorative board of the present disclosure has steps 1 to 4 below.
Step 1: A release layer is formed on a portion of one side of the first base material. In the one surface of the first base material, the region where the release layer is formed is defined as a first region, and the region where the release layer is not formed is defined as a second region. By forming a resin layer in the second region on the one surface side of the first substrate, a first laminate having the first substrate, the release layer and the resin layer is obtained. As the first base material, a water-soluble base material or a water-permeable base material is used.
Step 2: By stacking a second base material containing a resin-impregnated base material impregnated with an uncured thermosetting resin on the surface of the first laminate opposite to the side having the release layer, the second base material is 2 Laminates are obtained.
Step 3: Both surfaces of the second laminate are sandwiched between mirror plates and then hot-pressed to allow part of the uncured thermosetting resin to pass through the first substrate, and the first substrate A portion of the uncured thermosetting resin that has permeated the material is allowed to soak into the resin layer of the second region.
Step 4: Take out the second laminate from between the mirror plates to obtain a decorative plate.

Steps 1 to 4 will be described below with reference to FIGS. 3 and 4. FIG.

<Step 1>
In step 1, a release layer 20 is formed on part of one surface of the first base material 10 . In the one surface of the first base material, the region in which the release layer is formed is referred to as the first region, and the region in which the release layer is not formed is referred to as the second region. 3 and 4, symbol A1 corresponds to the first area, and symbol A2 corresponds to the second area.

In step 1, the embodiment of the relationship between the first area and the second area is the same as the embodiment of the relationship between the first area and the second area in the decorative laminate described above. As described above, examples of the relationship between the first region and the second region include the arrangement and area ratio of the first region and the second region.

The embodiment of the release layer formed in step 1 is the same as the embodiment of the release layer in the decorative laminate described above. For example, the release layer formed in step 1 preferably contains a cured product of an ionizing radiation-curable resin composition. The ionizing radiation-curable resin composition for the release layer is preferably cured at least before starting Step 3, and more preferably immediately after the release layer ink is applied in Step 1.

The release layer can be formed by applying a release layer ink containing components constituting the release layer onto the first base material, and drying and curing as necessary. Application means include general-purpose application means such as gravure coating, bar coating, roll coating, reverse roll coating, and comma coating.
In step 1, the release layer is preferably formed prior to the resin layer.
In order to improve the adhesion between the first base material and the release layer, a primer layer may be formed on the first base material before forming the release layer. In this case, the primer layer may be formed only in the first region, but is preferably formed in the first region and the second region.

Furthermore, in step 1, a resin layer is formed in the second region on the one surface side of the first substrate 10 . The resin layer may be formed only in the second region, or may be formed in the second region and the first region. When forming the resin layer in the first region, the resin layer is preferably formed on the release layer in the first region. In other words, when forming the resin layer in the first region, the resin layer is preferably formed on the side of the release layer opposite to the first substrate.
3 and 4, the primer layer 30 and pattern layer 40 correspond to the resin layer. In FIGS. 3 and 4, resin layers are formed in the second region and the first region.

The ratio of the area of the resin layer formed in the second region to the total area of the second region (area of the resin layer formed in the second region/total area of the second region) is preferably 0.80 or more, and 0.80 or more. 90 or more is more preferable, 0.95 or more is still more preferable, and 1.00 is most preferable.

In step 1, it is preferable to form at least one selected from a primer layer and a pattern layer as the resin layer.
When forming a primer layer and a pattern layer as the resin layer, it is preferable to form the primer layer and the pattern layer in this order from the first substrate side.

Embodiments of the primer layer and pattern layer formed in step 1 are the same as those of the primer layer and pattern layer in the above-described decorative laminate.
The resin layers such as the primer layer and the pattern layer can be formed by applying ink containing components constituting each layer, and drying and curing as necessary. Application means include general-purpose application means such as gravure coating, bar coating, roll coating, reverse roll coating, and comma coating.

In step 1, a water-soluble base material or a water-permeable base material is used as the first base material. The water-soluble base material or water-permeable base material serves as a support in forming the release layer and the resin layer in step 1. In addition, the water-soluble base material or water-permeable base material has the property of allowing part of the uncured thermosetting resin to permeate therethrough in step 3.

Embodiments of the water-soluble or water-permeable substrate used in step 1 are the same as the embodiments of the water-soluble or water-permeable substrate in the decorative laminate described above. Some of the embodiments of the water-soluble substrate or water-permeable substrate used in step 1 will be described below just in case.

In step 1, among the water-soluble base material and the water-permeable base material, the water-soluble base material is preferable in that the design formed by the pattern layer is less likely to be affected because of its less tint. Moreover, a polyvinyl alcohol film is preferable among water-soluble base materials.

Examples of water-permeable substrates include paper and fibers, and paper is preferable because it tends to have good coating suitability.

The basis weight of the paper as the water-permeable substrate is preferably 20 g/m ² or more and 100 g/m ² or less, more preferably 25 g/m ² or more and 80 g/m ² or less, and 30 g/m ² or more. It is more preferably 60 g/m ² or less.

A first laminate 100 having a first base material, a release layer, and a resin layer is obtained by the above-described step 1 .

<Step 2>
In step 2, as shown in FIG. 4, a resin-impregnated base material 201 impregnated with an uncured thermosetting resin is applied to the surface of the first laminate 100 opposite to the side having the release layer 20 . A second laminate 300 is obtained by stacking two substrates 200 .

<<Second base material>>
The second substrate includes a resin-impregnated substrate impregnated with an uncured thermosetting resin.
The resin-impregnated base material impregnated with an uncured thermosetting resin includes, for example, a base material that is easily impregnated with resin, such as a paper base material and a fiber base material, impregnated with an uncured thermosetting resin. . A resin-impregnated base material can be obtained, for example, by immersing a base material that is easily impregnated with a resin, such as a paper base material or a fiber base material, in a composition containing an uncured thermosetting resin.

A composition containing an uncured thermosetting resin may contain components other than the uncured thermosetting resin. Components other than the uncured thermosetting resin include additives such as UV absorbers and light stabilizers, thermoplastic resins, solvents and water. A composition containing an uncured thermosetting resin preferably contains water. That is, the composition containing uncured thermosetting resin is preferably an aqueous dispersion of uncured thermosetting resin.
The curable resin is preferably 50% by mass or more, more preferably 70% by mass or more, and 90% by mass or more with respect to the total resin amount of the composition containing an uncured thermosetting resin. is more preferable, and 100% by mass is even more preferable.
The uncured thermosetting resin is preferably a cured product of the thermosetting resin when the decorative board is completed. For example, an uncured thermosetting resin can be converted into a cured thermosetting resin by step 3 described below.

Embodiments of the paper base material and the fiber base material, which are the materials of the second base material, are the paper base material and the fiber base material that can be impregnated with the uncured thermosetting resin exemplified in the base material of the decorative board of the present disclosure described above. Similar to the substrate embodiment.
The embodiment of the uncured thermosetting resin that is the material of the second base material is the embodiment of the uncured thermosetting resin that is impregnated into the base material exemplified in the base material of the decorative sheet of the present disclosure described above. It is the same.

The second substrate 200 may be a laminated substrate having a resin-impregnated substrate 201 on a core layer 202 .
Embodiments of the core layer, which is the material of the second base material, are the same as the embodiments of the core layer exemplified in the above-described decorative laminate of the present disclosure.

<Step 3>
In step 3, the second laminate is sandwiched between mirror plates on both sides and is hot-pressed to allow part of the uncured thermosetting resin to pass through the first base material and also to pass through the first base material. A portion of the uncured thermosetting resin is impregnated into the resin layer of the second region.

In step 3, first, part of the uncured thermosetting resin is extruded from the resin-impregnated substrate. A portion of the uncured thermosetting resin that has passed through the first base material permeates into the resin layer of the second region. On the other hand, in step 3, the uncured thermosetting resin that has passed through the first base material hardly penetrates into the release layer in the first region. Therefore, the decorative sheet obtained by the manufacturing method of the decorative sheet of the present disclosure can generate a refractive index difference on the surface of the decorative sheet, and can improve the texture of the surface of the decorative sheet.

The uncured thermoset resin can be cured during step 3. The cured thermosetting resin is contained in, for example, the resin layer of the second region, the first substrate, and the second substrate.

The pressure of the hot press is preferably 10 kg/cm ² or more and 300 kg/cm ² or less, more preferably 50 kg/cm ² or more and 200 kg/cm ² or less, and 80 kg/cm ² or more and 150 kg/cm ² or less. It is even more preferable to have By hot-pressing within this range, the uncured thermosetting resin permeates the resin layer in the second region, and the permeation of the uncured thermosetting resin in the release layer in the first region is suppressed. A refractive index difference can be easily generated between the first region and the second region.
The hot press temperature is preferably 10° C. or higher and 300° C. or lower, more preferably 80° C. or higher and 200° C. or lower, and even more preferably 100° C. or higher and 180° C. or lower, in order to obtain excellent mechanical strength. .
The time for hot pressing can be appropriately adjusted depending on the thickness of the decorative board and the type of uncured thermosetting resin. The hot press time is, for example, preferably 1 minute or more and 60 minutes or less, more preferably 5 minutes or more and 30 minutes or less, and even more preferably 8 minutes or more and 20 minutes or less.

After step 3 is completed, the state and composition of the water-soluble substrate may differ from the original composition. For example, the water-soluble base material after step 3 may contain a hardened thermosetting resin contained in the resin-impregnated base material. Further, after Step 3 is completed, part of the water-soluble resin that constitutes the water-soluble base material may have soaked into the pattern layer and the primer layer of the second region.
After step 3 is completed, the condition and composition of the water permeable substrate may differ from the initial composition. For example, the water-permeable substrate after step 3 may contain a hardened thermosetting resin contained in the resin-impregnated substrate.

<Step 4>
In step 4, the second laminate is taken out from between the mirror plates to obtain a decorative plate.

It is preferable that the decorative sheet obtained by the decorative sheet manufacturing method of the present disclosure satisfy the following refractive index difference and altitude difference.

<Refractive index difference>
The outermost surface of the decorative sheet on the side of the first laminate is defined as the first surface. Among the layers constituting the first surface, n1 is the refractive index of the resin contained in the layer corresponding to the first region, and n2 is the refractive index of the resin contained in the layer corresponding to the second region. It is preferred that ≠n2.

By setting n1≠n2, a difference can be generated between the surface reflectance of the first region and the surface reflectance of the second region, so that a difference in brightness can be generated between the first region and the second region. can be made Due to this contrast difference, even if the difference in elevation between the first area and the second area is not sufficient, the texture of the surface of the decorative board can be improved.

The embodiment of the magnitude relationship between n1 and n2 in the method for manufacturing a decorative laminate of the present disclosure is the same as the embodiment of the magnitude relationship between n1 and n2 of the decorative laminate of the present disclosure. For example, |n1−n2| preferably has a lower limit of 0.02 or more and an upper limit of 0.20 or less.

The values of n1 and n2 can be adjusted according to the type of resin contained in the layer corresponding to the first region and the type of resin contained in the layer corresponding to the second region among the layers constituting the first surface. can. In the method for manufacturing a decorative board of the present disclosure, part of the uncured thermosetting resin that has passed through the first base material is impregnated into the resin layer in the second region, while in the first region, the release layer is the first. A difference between n1 and n2 is produced by suppressing penetration of the uncured thermosetting resin that has permeated the base material.

<Elevation difference>
The outermost surface of the decorative sheet on the side of the first laminate is defined as the first surface. Regarding the elevation of the first surface, it is preferable that the elevation difference between the elevation of the portion corresponding to the first region and the elevation of the portion corresponding to the second region is more than 1.0 μm and 5.0 μm or less.

If the elevation of the surface of the veneer is too uniform, the veneer tends to look like an artifact. Therefore, by setting the altitude difference to be more than 1.0 μm, it is possible to suppress the feeling of an artificial object and make it easier to feel like a natural object.
If there is too much difference in altitude on the surface of the decorative sheet, the appearance of unevenness based on the difference in refractive index on the surface of the decorative sheet may be impaired. Therefore, by setting the difference in elevation to 5.0 μm or less, it is possible to improve the feeling of unevenness on the surface of the decorative board.
In addition, if there is too much difference in altitude on the surface of the decorative board, dirt tends to accumulate in the recesses on the surface of the decorative board, and the antifouling property tends to decrease. For this reason, setting the difference in elevation to 5.0 μm or less is preferable in terms of easily improving the antifouling property.
The elevation difference is preferably 1.5 μm or more and 4.5 μm or less, more preferably 2.0 μm or more and 4.0 μm or less.

As for the magnitude relationship between the altitude of the location corresponding to the first region and the altitude of the location corresponding to the second region, the altitude of the first region may be higher, and the altitude of the second region may be higher. good too.
The altitude difference can be adjusted by the difference between the total thickness of the release layer and the resin layer formed in the first region and the total thickness of the resin layer formed in the second region.
In FIG. 4, symbol h indicates the altitude difference.

The method for manufacturing a decorative board according to the present disclosure can easily manufacture a decorative board with a good unevenness.
The conventional method for manufacturing a decorative board disclosed in Patent Document 3 requires a step of peeling off a release film, but the method for manufacturing a decorative board according to the present disclosure does not require a peeling process. When peeling off the release film, the peelability differs depending on the materials of the layers constituting the decorative board. For this reason, in the manufacturing method of Patent Document 3, it was necessary to change the manufacturing conditions for obtaining appropriate peelability each time the material was changed. Moreover, in the manufacturing method of Patent Document 3, when the predetermined material constituting the decorative board is changed, other materials may have to be changed in order to obtain appropriate peelability. Furthermore, in the production method of Patent Document 3, there is a problem that the release film is not good for the environment because it becomes dust.
On the other hand, the method for manufacturing a decorative laminate according to the present disclosure does not require a peeling step, so it is possible to suppress the above-described problems caused by peeling.

EXAMPLES Next, the present disclosure will be described in more detail with reference to examples, but the present disclosure is not limited by these examples.

1. Measurement and Evaluation The following items were measured and evaluated for the decorative laminates obtained in Examples and Comparative Examples. The environment for measurement and evaluation was set at a temperature of 23° C.±5° C. and a relative humidity of 40% to 65%.

1-1. Refractive index Of the layers constituting the first surface of the decorative board, n1 is the refractive index of the resin contained in the layer corresponding to the first region, and n2 is the refractive index of the resin contained in the layer corresponding to the second region. was measured according to JIS K 7142:2014 B method (Becke method by liquid immersion).

1-2. Feeling of Unevenness Under the illumination of a fluorescent lamp, the decorative sheets obtained in Examples and Comparative Examples were visually evaluated by 20 random adults as to whether or not they had a sense of unevenness. Then, evaluation was made according to the following criteria.
A: 18 or more people answered that the product had a design with a high three-dimensional effect.
B: 11 people or more and 17 people or less answered that they had a design with a high three-dimensional effect.
C: 6 or more and 10 or less of the respondents answered that they had a design with a high three-dimensional effect.
D: The number of persons who answered that it had a design with a high three-dimensional effect was 5 or less.

1-3. Elevation difference With respect to the first surface of the decorative board, the elevation of the location corresponding to the first region and the elevation of the location corresponding to the second region were measured. Measurement was performed at 10 points in each area, and the average value of the 10 points was taken as the altitude of each area. The elevation difference was calculated by subtracting the elevation of the location corresponding to the second region from the elevation of the location corresponding to the first region.

1-4. Stain Resistance A straight line was drawn on the surfaces of the decorative boards obtained in Examples and Comparative Examples with a black oil-based pen (magic ink manufactured by Teranishi Kagaku Kogyo Co., Ltd., product number: ML-T1) conforming to JIS S60377. After leaving it to stand for 5 minutes, it was wiped dry, and the degree of writing marks left on the surface of the decorative board was visually evaluated according to the following criteria.
A: No handwriting marks were observed.
B: Although some writing marks were observed, they were of a degree of practically no problem.
C: A handwriting trace was confirmed.

2. Preparation of release layer ink 60 parts by weight of ionizing radiation-curable monomer (Aronix M400, manufactured by Toagosei Co., Ltd.), 0.9 parts by weight of reactive silicone (X-22-164B, manufactured by Shin-Etsu Chemical Co., Ltd.), and methyl ethyl ketone (Maruzen Petrochemical Co., Ltd.) was stirred for 1 hour at 2000 rpm using a process homogenizer PH91 (manufactured by SMT Co., Ltd.) to prepare a release layer ink.

3. Production of decorative board [Example 1]
As the first base material, a water-soluble film (polyvinyl alcohol film, Mitsubishi Chemical Co., trade name: Hi-Selon C-300, thickness 40 μm) was prepared.
Part of one side of the water-soluble film is coated with the release layer ink of “2” by gravure coating, and cured by electron beam irradiation of 3 Mrad at an acceleration voltage of 165 kV to obtain a film having a thickness of 3 μm. A release layer was formed. The pattern of the release layer was a pattern in which independent portions each having a width of 30 μm and a length of 50 mm were randomly arranged. The region where the release layer is formed is the first region, and the region where the release layer is not formed is the second region.
Next, on the first region and the second region, a primer layer ink containing an acrylic urethane resin was applied and dried to form a primer layer with a thickness of 1 μm.
Next, a first pattern layer ink containing an acrylic resin and a colorant was applied to a portion corresponding to the first region on the primer layer and dried to form a first pattern layer having a thickness of 3 μm. Further, a second pattern layer ink containing an acrylic resin and a colorant was applied to a portion corresponding to the second region on the primer layer and dried to form a second pattern layer having a thickness of 3 μm. A wood grain pattern is formed by the first pattern layer and the second pattern layer.
Through the above steps, a first laminate having a first substrate (water-soluble film), a release layer, and a resin layer (primer layer and pattern layer) was obtained.

Next, using an impregnation device, a base material (titanium paper base paper for building materials, product name “PM-67P” manufactured by KJ Specialty Paper Co., Ltd., basis weight: 80 g / m ² , thickness: 100 μm) was coated with the following composition. Impregnated with things. Impregnation was such that the rate of uncured composition was 80 g/m ² (dry). Then, by drying, a resin-impregnated paper was obtained. The drying described above was terminated when the surface of the resin-impregnated paper became tacky. That is, water was allowed to remain inside the resin-impregnated paper.
Next, the resin-impregnated paper and the core layer described below were laminated to obtain a second substrate including the core layer and the resin-impregnated paper.
<Liquid uncured composition of thermosetting resin>
・Melamine formaldehyde resin 60 parts by mass ・Water 35 parts by mass ・Isopropyl alcohol 5 parts by mass <Core layer>
Two sheets of phenolic resin-impregnated core paper (manufactured by Ohta Sangyo Co., Ltd., Ohta Core) with a basis weight of 245 g/m ² obtained by impregnating kraft paper with a liquid uncured resin composition made of phenolic resin are stacked. Something.

Then, the surface of the first laminate opposite to the side having the release layer and the resin-impregnated paper side surface of the second substrate were laminated to obtain a second laminate.

The second laminate was sandwiched between two mirror plates and heat-molded using a hot press under the conditions of a pressure of 100 kg/cm ² and a molding temperature of 150° C. for 10 minutes.
During this step, part of the uncured thermosetting resin permeates the water-soluble film, and part of the uncured thermosetting resin that permeates the water-soluble film is the primer layer of the second region and the second region. It permeated into two pattern layers. In the first region, since the release layer suppresses penetration of the uncured thermosetting resin, the uncured thermosetting resin hardly penetrates into the primer layer and the first pattern layer of the second region.
Moreover, after the completion of this step, most of the thermosetting resin had been cured.
Next, the second laminate was taken out from between the mirror plates to obtain a decorative plate of Example 1.

[Comparative Example 1]
A base material (titanium paper base paper for building materials, trade name “PM-67P” manufactured by KJ Specialty Paper Co., Ltd., basis weight: 80 g/m ² , thickness: 100 μm) was coated with printing ink (manufactured by DIC Graphics Co., Ltd., "Ode SPTI") was used to form a 3 μm-thick first decorative layer (vessel portion of wood grain) and a second decorative layer (wood surface portion of wood grain) by gravure printing.
Next, on the first decorative layer, the following curable resin composition 1 for forming the first cured material layer is printed and irradiated with an electron beam (applied voltage: 165 KeV, 3 Mrad (30 kGy)) to cure. , to obtain a laminate A formed by forming a first cured material layer having a thickness t1 of 15.0 μm.
Next, the laminate A was impregnated with the following curable resin composition for forming the second cured material layer, and dried to obtain a laminate B (the amount of the cured resin composition when dried was 80 g / m ² impregnation).
Next, on the surface of the laminate B opposite to the substrate (the surface having the uncured second cured product layer), the following release film is laminated, and the surface of the laminate B on the substrate side is laminated. , Reinforcement layer (3 phenolic resin-impregnated core papers (Ohta Core, manufactured by Ohta Sangyo Co., Ltd.) with a basis weight of 245 g / m ² obtained by impregnating kraft paper with a liquid uncured resin composition made of phenolic resin A layered product C was obtained by stacking the layers.
Next, both sides of the laminate C are sandwiched between mirror plates (a mirror plate is placed on the reinforcing layer side and an embossed plate is placed on the release film side), and a heat press is used to press the laminate at a molding temperature of 150° C. and a molding pressure of 100 kg/cm ² . For 10 minutes, heat and pressure molding was performed. After molding, the laminate C was taken out from between the two mirror plates, and the release film was peeled off from the laminate C to obtain a decorative board of Comparative Example 1.
In addition, when peeling and removing the release film from the laminate C, the second cured material layer on the first cured material layer of the second cured material layer was removed together with the release film, and the recessed first region was formed. . In addition, a convex second region where the second cured material layer remained was formed in a portion where the first cured material layer did not exist.

[Comparative Example 2]
A decorative board of Comparative Example 2 was obtained in the same manner as in Comparative Example 1, except that the first cured product layer was not formed. The decorative board of Comparative Example 2 has a second cured material layer with a uniform thickness on the entire surface of the first decorative layer and the second decorative layer of the base material, and there is no distinction between the first region and the second region. It is.

According to the method for manufacturing a decorative board of Example 1, a decorative board having excellent unevenness could be manufactured by a simple method.
On the other hand, the method for producing a decorative board of Comparative Example 1 can obtain a decorative board having an excellent unevenness, but it has a peeling step, so it is difficult to adjust the manufacturing conditions for obtaining appropriate peelability. It cannot be said that it can be manufactured easily. In the method for manufacturing the decorative board of Comparative Example 2, since the surface of the obtained decorative board did not have regions with different refractive index differences, the feeling of unevenness was poor.

10 First substrate 11 Water-soluble substrate 20 Release layer 30 Primer layer 40 Pattern layer 41 First pattern layer 42 Second pattern layer 100 First laminate 200 Second substrate 201 Resin-impregnated substrate 202 Core layer 300 2 Laminate 80 Base material 90 Layer 500 Decorative plate A1 First region A2 Second region S1 First surface

Claims (17)

A method for manufacturing a decorative board, comprising the following steps 1 to 4.
Step 1: A release layer is formed on a portion of one side of the first base material. In the one surface of the first base material, the region where the release layer is formed is defined as a first region, and the region where the release layer is not formed is defined as a second region. By forming a resin layer in the second region on the one surface side of the first substrate, a first laminate having the first substrate, the release layer and the resin layer is obtained. As the first base material, a water-soluble base material or a water-permeable base material is used.
Step 2: By stacking a second base material containing a resin-impregnated base material impregnated with an uncured thermosetting resin on the surface of the first laminate opposite to the side having the release layer, the second base material is 2 Laminates are obtained.
Step 3: Both surfaces of the second laminate are sandwiched between mirror plates and then hot-pressed to allow part of the uncured thermosetting resin to pass through the first substrate, and the first substrate A portion of the uncured thermosetting resin that has permeated the material is allowed to soak into the resin layer of the second region.
Step 4: Take out the second laminate from between the mirror plates to obtain a decorative plate. 2. The method of manufacturing a decorative laminate according to claim 1, wherein in said step 1, said resin layer is also formed on said release layer in said first region. 3. The method of manufacturing a decorative laminate according to claim 1, wherein in said step 1, at least one selected from a primer layer and a pattern layer is formed as said resin layer. 4. The method for producing a decorative laminate according to claim 1, wherein in said step 1, a water-soluble base material is used as said first base material. The method for producing a decorative board according to claim 4, wherein the water-soluble base material is a polyvinyl alcohol film. 4. The method for producing a decorative board according to claim 1, wherein in said step 1, a water-permeable base material is used as said first base material. The method for producing a decorative board according to claim 6, wherein the water-permeable base material is paper having a basis weight of 20 g/ ^m2 or more and 100 g/ ^m2 or less. The method for producing a decorative laminate according to any one of claims 1 to 7, wherein the release layer contains a cured product of an ionizing radiation-curable resin composition. The method for producing a decorative laminate according to any one of claims 1 to 8, wherein the second base material in step 2 is a laminated base material having the resin-impregnated base material on a core layer. The outermost surface of the decorative sheet on the side of the first laminate is defined as a first surface. Among the layers constituting the first surface, n1 is the refractive index of the resin contained in the layer corresponding to the first region, and n2 is the refractive index of the resin contained in the layer corresponding to the second region. 10. The method for manufacturing a decorative laminate according to claim 1, wherein n1≠n2. The method for producing a decorative laminate according to claim 10, wherein |n1-n2| is 0.02 or more and 0.20 or less. The outermost surface of the decorative sheet on the side of the first laminate is defined as a first surface. 2. Regarding the elevation of the first surface, the elevation difference between the elevation of the portion corresponding to the first region and the elevation of the portion corresponding to the second region is more than 1.0 μm and 5.0 μm or less. 12. A method for manufacturing a decorative board according to any one of -11. A decorative laminate having one or more layers on a substrate,
The decorative plate has a first region and a second region in the plane,
A decorative board that satisfies the following conditions 1 and 2 when the outermost surface of the side of the decorative board having one or more layers is defined as the first surface.
<Condition 1>
Among the layers constituting the first surface, n1 is the refractive index of the resin contained in the layer corresponding to the first region, and n2 is the refractive index of the resin contained in the layer corresponding to the second region. , n1≠n2.
<Condition 2>
Regarding the elevation of the first surface, the elevation difference between the elevation of the location corresponding to the first region and the elevation of the location corresponding to the second region is more than 1.0 μm and 5.0 μm or less. 14. The decorative board according to claim 13, wherein in condition 1, |n1-n2| is 0.02 or more and 0.20 or less. Claim 13 or, wherein, as the one or more layers, a release layer is provided in a portion corresponding to the first region, and at least one selected from a primer layer and a pattern layer is provided in a portion corresponding to the second region. 15. The decorative board according to 14. 16. The decorative board according to claim 15, which has at least one selected from a primer layer and a pattern layer on the side of the release layer opposite to the base material. The decorative board according to claim 15 or 16, wherein the release layer contains a cured product of an ionizing radiation-curable resin composition.

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